Asymmetric and Diastereoselective Conjugate Addition Reactions: C–C Bond Formation at Large Scale

Howell, Gareth P.

doi:10.1021/op200381w

Cited by 116 publications

(72 citation statements)

References 64 publications

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“…The Suzuki-Miyaura reaction uses arylboronic acid reagents, which are relatively stable in air and readily available 5 . The generally favourable reactivity profile and high atom economy of boronic acids makes them highly desirable reaction partners in synthetic and medicinal chemistry 6 , particularly when compared with alternative sp 2 -hybridized organometallic reagents used in C-C bond-forming reactions 7 .…”

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confidence: 99%

Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

Sidera

Fletcher

2015

Nature Chem

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Csp(2)-Csp(2) cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp(2)-Csp(3) cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp(2)-Csp(3) bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

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confidence: 99%

Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

Sidera

Fletcher

2015

Nature Chem

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“…The versatility of catalytic approaches to C-C bond formation using chiral Lewis acids is also evident in conjugate addition reactions [169,170] of Michael acceptors [171][172][173], including the asymmetric vinylogous Michael addition (Scheme 37) for which regioselectivity is a common challenge. For reactions of α,β-unsaturated ketones in water, a scandium(III) triflate/chiral bipyridine complex has been advanced as offering new opportunities for asymmetric synthesis [174,175]; these "green" reaction processes do not occur with transition metal triflates, which are inhibited by coordination with water, but they are highly effective even at low catalyst loadings with Sc(OTf) 3 at room temperature (Scheme 38).…”

Section: Michael Reactionsmentioning

confidence: 99%

The Future of Catalysis by Chiral Lewis Acids

Sha

Deng

Doyle

2015

Topics in Organometallic Chemistry

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Even with the rapidly expanding popularity of organocatalysts for organic reactions, chiral metal-based Lewis acid catalysts continue to have a uniquely important role in asymmetric reactions. Their broad applicability to cycloaddition and condensation reactions based on close encountered associations of Lewis base reactants with these chiral Lewis acid catalysts provides architecturally confined complexes that provide high stereocontrol in their chemical reactions.

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“…In particular, the development of organocatalytic asymmetric Michael reactions of carbonyl compounds with nitroalkenes has garnered great interest in recent years. [30][31][32][33][34] However, asymmetric Michael reactions using monoester or acid directly as prenucleophiles have never been reported. The use of pyrazole amides as special Michael donors to react with nitroolefins, reported by Barbas III and co-workers, and the use of quinine derived urea catalysts gave the desired product with high dr and ee value.…”

Section: Introductionmentioning

confidence: 99%

Organocatalytic asymmetric Michael reaction with acylsilane donors

et al. 2013

Org. Biomol. Chem.

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We have developed an organocatalytic asymmetric Michael reaction of acylsilane through the selection of acylsilane substrates and organocatalysts, thus creating a rare example of acylsilane α-alkylation with a chiral guanidine catalyst, which afforded products in good yields and high stereoselectivity. The corresponding adducts described here have also been demonstrated to be useful in the synthesis of unnatural amino acids and biologically active compounds.

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Asymmetric and Diastereoselective Conjugate Addition Reactions: C–C Bond Formation at Large Scale

Cited by 116 publications

References 64 publications

Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

The Future of Catalysis by Chiral Lewis Acids

Organocatalytic asymmetric Michael reaction with acylsilane donors

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